Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.

Addition reaction of nitrones on the reconstructed Si(100)-2 x 1 surface

The reaction of nitrone, N-methyl nitrone, and their hydroxylamine tautomers (vinyl-hydroxylamine and N-methyl vinyl-hydroxylamine) on the reconstructed Si(100)-2 x 1 surface has been investigated by means of hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The calculations predicted that both of the nitrones should react with the surface dimer via facile concerted 1,3-dipolar cycloaddition leading to 5-member-ring compounds. The reaction of hydroxylamine tautomers on the Si(100) surface follows pi-complex (intermediate) mechanism. For the reaction of N-methyl vinyl-hydroxylamine, the pi-complex intermediate undergoes [2+2] cycloaddition leading to a 4-member-ring compound. But in the reaction of vinyl-hydroxylamine, the intermediate undergoes H-migration reaction ("ene" reaction) resulting in the oxime-terminated Si surface. All the surface reactions result in the hydroxyl-terminated silicon surfaces, which are very useful for the further modification of the semiconductor.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

中低纬度变化磁场的暴时特征研究

Magnetic storm is a kind of severe disturbances in the whole solar-earth electromagnetic space. It has significant effects on communication, electric power, oil transport pipe and human activities in space. Therefore, magnetic storms are worth for applications systems, not only being a favorable issue for scientists. In this paper, the spatial and temporal distributions of the magnetic fields produced by the magnetosphere-ionosphere current systems during storms are studied. Four parts are included in this paper decomposion of different disturbances with different origins, topological structure of the ring current, the asymmetric characteristics of the ring current, and the statistic peculiarities of the day-to-day variability (DTD) of Sq. 1 The decomposition of magnetic disturbances at mid-low latitudes and its evolutions during storms Transient variations in the geomagnetic field recorded at mid-low latitudes mainly include the storm-time variation (Dst), solar quiet daily variation (Sq) and disturbance daily variation (SD). With the data of the geomagnetic meridian chain observatories in China, 25 storms during the period of 1997 to 1999 have been analyzed. According to the features of different variations, a method of “three-steps decomposition” is developed by using the method of Natural Orthogonal Components (NOC), Correlation Analysis and Fourier Analysis to separate those three components in turn. The results show that, the first eigenmode by the MNOC clearly describing the special distribution and temporal evolution of storm-time variation, in addition, Correlation Analysis and Fourier Analysis offer a useful method to extract the Sq and SD variations. The latitudinal shift of the Sq current focus seems to be the principal reason of the day-to-day variaitons in the daily range of Sq. The magnitude of SD reaches a maximum during the main phase, and then gradually decreases. 2 The topology structure of the ring current during storms Both the mechanism of the ring current and the geomagnetic data suggest that the central plane of the ring current is declining to the geomagnetic equator plane with a tilt angle δ. Using the H and Z component data at two stations in a meridian chain, we deduce a new parameter describing the invariable peculiarity of different storms. Then the δ angle is calculated by using the data from a meridian chain and tested with the ERC model. Finally the deduced tilt angles are used to modify Dst index. 3 The asymmetric characteristics of the ring current during storms The variations of the geomagnetic field at mid-low latitudes show a significant dawn-dusk asymmetry, resulting from the superposition of the fields from the symmetric ring current and the partial ring current. On the basis of the data from the 20°E, 30°E meridian chains and 30°N latitudinal chain, the dawn-dusk asymmetry is investigated by using three methods, namely, statistic analysis, ring current model calculation and typical event analysis. This characteristic implies the asymmetry of the spatial distribution of the ring current. In addition, during the main phase after the sudden commencement (SC), H field increases and reaches maximum around noontime, implying the effect of the Chapman-Ferraro current. 4 The statistic characteristics of the day-to-day variability and its mechanism The day-to-day variability of the geomagnetic Sq field is studied by using the magnetic data from a meridian chain of magnetometers along 120° E longitude. The method of NOC is applied to separate the Sq variation from complicated disturbances. The first eigenmode with the largest eigenvalue represents fairly well the Sq variation with a conspicuous day-to-day variability in the daily range. For the stations on the same north- or south-side of the Sq current system focus, the day-to-day variations show a positive correlation. In contrast, for the stations on the different sides of the Sq focus, they show a negative correlation, suggesting an important role of latitudinal shift of the Sq current system focus to the day-to-day variability of the Sq daily range. The Sq daily range is correlated with the magnetic indices Ap and Dst in a peculiar way: on some severe disturbed days, noticeably enhancements of the Sq are observed, implying increases of the ionospheric conductivities and/or tidal wind velocities; on other severe disturbed days, however, dramatically reduced Sq variations occur, suggesting dominant effects of the ‘disturbance dynamo’ process.

Removal of NO by microwave discharge with the addition of CH4

Removal of NO by a continuous microwave discharge at atmospheric pressure with the addition of CH4 is reported. The conversion of NO to N-2 is approximately 80%, and the energy efficiency is up to 0.55 g-NO/kWh. The effects of CH4 addition and three discharge modes on NO conversion and energy efficiency are investigated. The dependence of NO conversion on experimental time is also observed.

Effect of syngas addition on lower alkene production by the oxidative cracking of hexane

The lower alkene production by the gas-phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of hexane (C6) with added syngas was investigated. The addition of syngas to the COC process could effectively enhance the selectivity to lower alkenes and decrease the selectivity to COx, because of the preferential reaction between O-2 with H-2 contained in the syngas, whereas it has little effect on the conversion of C6 and product distribution in the GOC process. The high selectivity to lower alkenes of 70% and low selectivity to CO, of 6% at C6 conversion of 66% were achieved over 0.1% Pt/MgAl2O4 catalyst. The COC process of C6 combined with the syngas in the feed could directly produce a gas mixture of lower alkenes, H-2, and CO, which usually is a suitable feedstock for the hydroformylation process.